JPH04367202A - Fe-based amorphous alloy thin belt having excellent magnetically soft characteristic and its manufacture - Google Patents

Abstract

PURPOSE:To provide a method wherein a hysteresis loss and an iron loss are improved sharply in an Fe-based amorphous alloy thin belt and to provide the Fe-based amorphous alloy thin belt manufactured by the method and ultralow in loss. CONSTITUTION:Both faces of an Fe-based amorphous alloy thin belt which has been manufactured by a multiple slit nozzle method and whose sheet thickness is at 45mum or higher are etched and removed; a hysteresis loss at 1.3T is improved to be at 0.04W/kg or lower. In addition, a magnetic-domain segmentation treatment is executed; an iron loss at 50Hz and 1.3T is improved to be at 0.08W/kg or lower. In the Fe-based amorphous alloy thin belt, its hysteresis loss and its iron loss are extremely low although its sheet thickness is large. Consequently, when it is used for an electric apparatus such as an iron core for a power transformer or the like, it contributes toward enhancing its efficiency largely.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is based on Fe, which has a high saturation magnetic flux density and excellent soft magnetic properties, and can be applied to power transformers, high frequency transformer cores, magnetic circuit yokes, saturable reactor cores, magnetic sensors, etc. It concerns amorphous alloys.

0002

[Prior Art] Fe produced by single roll quenching method
Basic amorphous alloy ribbons have excellent electromagnetic properties and high productivity, so they are attracting attention as iron core materials for power transformers, and are even being put into practical use in some areas. However, compared to the grain-oriented silicon steel sheets commonly used today, the material cost is high;
Progress in commercialization has been slower than initially expected because the plate thickness is too thin. Among the practical problems specific to these amorphous alloys, the issue regarding plate thickness was addressed in Japanese Patent Publication No. 63-40629.
50μ by the multi-slit nozzle method disclosed in the publication.
A thick-walled material with a thickness exceeding 100 m has been developed, and the problem has almost been solved technically. In addition, in terms of material costs, productivity has more than doubled with the multi-slit nozzle method mentioned above, and the cost difference with silicon steel sheets has narrowed due to the development of technology that enables the use of low-cost raw materials. .

[0003] Nevertheless, the penetration rate of amorphous alloy core transformers is still low. One of the reasons for this is the remarkable improvement in core loss of silicon steel sheets in recent years. The reason why the iron loss of amorphous alloys has remained almost flat is that the iron loss of amorphous alloys is originally extremely low, about 1/5 of that of silicon steel sheets, so efforts to reduce iron loss have been difficult. In addition, effective measures for reducing iron loss in silicon steel sheets have little effect on amorphous alloys. That is, typical methods for reducing iron loss in silicon steel sheets include crystal orientation control, crystal grain size control, thinning, increasing the amount of Si, laser irradiation, and applying tension. By optimizing these factors, today, although on a laboratory scale, 50Hz
, iron loss W13/50 at 1.3T is 0.16 to 0
．． Nozawa et al. (
Materials from the 51st meeting of the Japanese Society of Applied Magnetics (1987, p. 3) and Nishiike et al. (p. 21). This iron loss value of silicon steel sheet is comparable to that of an average Fe-based amorphous alloy ribbon, and even when compared to the highest level value of 0.1 W/kg, the difference is much larger than before. It's shrinking.

[0004] Among the above methods that have been shown to be effective for silicon steel sheets, thinning, laser irradiation, and tension application are potentially applicable to improving the core loss of amorphous alloys. However, the result of application was that there was no effect at all or only a slight effect on a thin ribbon with a thickness of 30 μm. The reason for this is that in an amorphous alloy, which originally has a small eddy current loss ratio, a decrease in eddy current loss and an increase in hysteresis loss are offset. Of the three methods mentioned above, laser irradiation was effective for thick amorphous alloys.

Regarding the effect of laser irradiation on thick amorphous alloys, T. Sato et al. have already reported (1
Published by North-Holland in 985 Pro
ceedings of the Fifth Inte
National Conference on R
apidly Quenched Metals Vo
lume 2 page 1643). They found that the greater the thickness of the amorphous alloy ribbon, the greater the reduction in iron loss due to laser irradiation (see Figure 4), and that this is because the greater the thickness, the greater the abnormal eddy current loss. I have to. However, as shown in Figure 4, the iron loss value of thick-walled materials after laser irradiation is not lower than that of thin-walled materials, and when the thickness is 30 μm or more, W
The value of 13/50 was not improved to about 0.1 W/kg or less.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an Fe-based amorphous alloy ribbon with significantly improved core loss and a method for producing the same.

[0007]

[Means and operations for solving the problems] The gist of the present invention is as follows. (1) 45 manufactured using a multi-slit nozzle
In an Fe-based amorphous alloy ribbon having a thickness of μm or more, the surface layer of the amorphous alloy ribbon has a thickness of at least 0.5 μm.
By removing the thickness from both the front and back sides,
Hysteresis loss at maximum magnetic flux density of 1.3T is 0.0
A method for producing an Fe-based amorphous alloy ribbon with excellent soft magnetic properties, characterized in that the magnetic strength is 4 W/kg or less.

(2) The method for producing an Fe-based amorphous alloy ribbon with excellent soft magnetic properties as described in the preceding item 1, characterized in that the surface layer of the ribbon is removed by chemical etching. (3) An Fe-based amorphous alloy ribbon with excellent soft magnetic properties produced by the method described in 1 and 2 above. (4) The thickness of the plate manufactured by the method described in section 1 above is 30μ.
By performing magnetic domain refining treatment on a Fe-based amorphous alloy ribbon with a diameter of 50Hz or more, the iron loss at 1.3T at 50Hz can be reduced to 0.0.
A method for producing an Fe-based amorphous alloy ribbon with excellent soft magnetic properties, characterized in that the magnetic strength is 8 W/kg or less.

(5) The method for producing an Fe-based amorphous alloy ribbon having excellent soft magnetic properties as described in the above item 4, wherein the method of magnetic domain refining is pulsed laser irradiation. (6) The method for producing an Fe-based amorphous alloy ribbon with excellent soft magnetic properties as described in item 4 above, wherein the magnetic domain refining method is by forming grooves parallel to the width direction of the ribbon. (7) The F having excellent soft magnetic properties as described in the preceding item 4, characterized in that the method of magnetic domain refining is the introduction of mechanical strain.
A method for producing an e-based amorphous alloy ribbon.

(8) An Fe-based amorphous alloy ribbon with excellent soft magnetic properties produced by the method described in item 4 above. In the present invention, when the surface layer of a thick Fe-based amorphous alloy ribbon with a thickness of 50 μm or more produced by the multi-slit nozzle method is removed by chemical etching, the hysteresis loss is reduced as shown in FIG. It decreases rapidly with the amount of thickness removed, and the plate thickness is 50μ.
This was completed based on the finding discovered for the first time by the present inventors that below m, a substantially constant extremely small value is maintained. On the other hand, in the case of an amorphous alloy ribbon with a thickness of 30 μm produced by the general single-slit nozzle method, the hysteresis loss slightly decreases in the early stage of etching when the thickness is removed by the same chemical etching. However, the achieved hysteresis loss value is larger than that of thick-walled materials, and does not reach 0.04 W/kg or less. Furthermore, it is clear from FIG. 1 that the plate thickness range in which the hysteresis loss is constant is extremely narrow. That is, by etching a thick amorphous alloy ribbon produced by the multi-slit nozzle method, an extremely low hysteresis loss that cannot be achieved with conventional Fe-based amorphous alloy ribbons can be obtained. In order to obtain a hysteresis loss of 0.04 W/kg or less by etching, the initial plate thickness must be 45 μm or more, so in the present invention, the lower limit of the thickness of the ribbon is set to 45 μm.
limited to. Further, since the improvement in hysteresis loss is small unless the amount of plate thickness removed by etching is 0.5 μm or more on both surfaces, the lower limit of the amount removed is defined as at least 0.5 μm on both the front and back surfaces.

Furthermore, extremely low iron loss can be achieved by applying a magnetic domain refining technique to a Fe-based amorphous alloy ribbon having a thickness of 30 μm or more that has been subjected to hysteresis loss reduction treatment by etching. As a means for magnetic domain refining, known methods such as laser irradiation, formation of grooves parallel to the ribbon width direction, or introduction of linear mechanical strain can be applied. An important point to keep in mind when subdividing magnetic domains is to minimize the increase in hysteresis loss. Regarding the laser irradiation method, the power of the laser is reduced compared to the conventional case without etching. Alternatively, the distance between the laser spots can be set wide. Specifically, when controlling by laser power, the spot spacing is set to about 1/2 or less of the proper value without etching, and when controlling the spot spacing, it is set to about twice or more than the proper value without etching. In the present invention, it is difficult to uniquely define appropriate irradiation conditions. There are three methods: annealing, etching, and laser irradiation.
This is because the optimum irradiation conditions differ depending on the order of the processes. There are six types of process orders: Specifically, ■annealing, etching, laser irradiation, ■annealing, laser irradiation, etching, ■laser irradiation, annealing, etching, ■laser irradiation, etching, annealing, ■etching, laser irradiation, annealing, ■etching, There are six types: annealing and laser irradiation. Among these, three of them, ■, ■, ■, when comparing the best characteristics,
It was inferior to ■, ■, and ■. Therefore, in the present invention, ■
We recommend the following processes: ,■,■.

Next, preferable laser irradiation conditions for the processes (1), (2), and (3) will be specifically shown using the size of the laser spot as an index. Here, the laser spot refers to an irradiation mark formed on the surface of the ribbon by laser irradiation. In process (1), ie, annealing→etching→laser irradiation, irradiation is performed under irradiation conditions such that the diameter of the laser spot is 5 to 50 μm. Expressing this condition in terms of laser power, when using a laser beam with a diameter of 0.5 mm or less, it corresponds to approximately 0.01 to 0.5 W. As a result, the iron loss is approximately 10 when an amorphous alloy ribbon with an initial thickness of 45 μm or more is annealed and then etched to a thickness of 30 μm.
~30%, and when the initial plate thickness is 65 μm and then etched to 50 μm after annealing, the improvement is approximately 20 to 50%. In processes (2) and (2), irradiation is performed under stronger conditions than in (2). When the favorable conditions are expressed by the diameter of the spot,
It is 50 to 200 μm.

Similarly, when adopting the groove forming method as a magnetic domain refining method, it is important to suppress the increase in hysteresis loss as much as possible by making the depth of the grooves shallower than before or widening the interval between the grooves. be. Furthermore, when introducing mechanical strain, it is necessary to reduce the magnitude of the strain and to widen the interval between linear strains to at least twice the appropriate value for the conventional method.

The reason why the thickness of the plate after etching to which the magnetic domain refining process is applied is set to 30 μm or more will be explained with reference to FIG. In FIG. 2, marks △ and ▲ indicate changes in iron loss W13/50 when laser irradiation was performed under optimal conditions on a conventional thin ribbon that had been annealed and etched. From the figure, before irradiation (
It can be seen that the improvement in iron loss between △) and after irradiation (▲) is slight. On the other hand, it can be seen that in the material having a plate thickness of 30 μm or more after etching according to the present invention, the iron loss improvement effect due to irradiation is remarkable. The iron loss improvement effect is achieved when the plate thickness after etching is 3
Even if it is less than 0 μm, it is larger than the conventional etched thin ribbon (not shown), and the iron loss W13/5
0 indicates a value smaller than 0.08 W/kg, but since the removed plate thickness is large, there is a problem in economic efficiency. Therefore, the thickness of the plate subjected to the magnetic domain refining treatment was limited to 30 μm or more.

The amorphous alloy targeted by the present invention is an Fe-based amorphous alloy. Specifically, Fe is the main component, B,
It is an amorphous alloy containing Si and C as subcomponents. Here Fe
is an essential element to obtain a high saturation magnetic flux density, and the subcomponent is an essential element to form an amorphous state. The preferred composition ranges of each constituent element are: Fe: 75-82 (atomic %, same hereinafter), B: 7-16, Si: 4-18, C
:0 to 4. To this basic composition, in order to improve practical properties such as saturation magnetic flux density, magnetic permeability, thermal stability, corrosion resistance, and film forming properties, a total of 20 atomic % or less of Co or Ni, or 5 atomic % or less of Co or Ni is added. Mo, Cr, Mn
, Nb, W, Ta, V, and Sn can be added.

Next, the embodiments of the present invention will be further explained. The multi-slit nozzle used in the present invention is a nozzle having two or more slit-like openings as shown in FIG. If this multi-slit nozzle is not used, a thick amorphous alloy that satisfies the required properties required for the iron core material cannot be obtained. Therefore, the manufacturing method employed in the present invention is limited to the multiple slit nozzle method. Also, the initial plate thickness was changed to 4
The reason why it is specified to be 5 μm or more is that if it is less than 45 μm, the effect of surface roughness remains even after etching, and the reduction in hysteresis loss is small, so the target hysteresis loss (0.04 W/kg or less) at 1.3 T is achieved. As a result, even if magnetic domain refining processing is performed, the iron loss W13/50
This is because it does not reduce to 0.08 W/kg or less.

The etching of the present invention is performed using a chemical method, for example, 5vol. A hydrogen peroxide solution containing % hydrogen fluoride can be used. Annealing is performed in an inert gas atmosphere, when the crystallization temperature of the amorphous alloy is Tx, Tx ~
It is carried out at a temperature of Tx-180°C for 5 to 120 minutes.

[0018]

【Example】

Example 1 An amorphous alloy ribbon having a thickness of 53 μm and a width of 25 mm was produced from an alloy having the composition Fe80.5Si6.5 B12C1 (atomic %) by a single roll quenching method using a roll made of Cu. In manufacturing the ribbon, a nozzle was used in which three slit-shaped openings each having a width of 0.4 mm were arranged at an interval of 1 mm. However, the roll circumferential speed was 24 m/s. This amorphous alloy ribbon was annealed in a magnetic field at 380° C. for 60 minutes in an N2 gas atmosphere, and then etched to remove a total thickness of 10 μm from both the front and back surfaces. The etching solution used here was 5 vol. of hydrogen fluoride. % hydrogen peroxide solution. The hysteresis loss of the ribbon with the surface layer removed was found to be 0.020.
It was W/kg. The hysteresis loss was determined from the frequency dependence of iron loss measured using a single-plate tester. This ribbon was irradiated with a YAG pulse laser. The irradiation conditions are a YAG pulse laser with a beam diameter of 0.1 mm and a power of 0.1
W, the beam was scanned in the width direction of the ribbon so that the spot spacing was 250 μm and the dot row spacing was 5 mm. Iron loss W13/50 measured with a veneer tester is 0.053W/
It was kg. This iron loss value is superior to the iron loss value of 0.098 W/kg obtained by laser irradiation on a Fe-based amorphous alloy having the same plate thickness of 33 μm without etching.

Example 2 An amorphous alloy ribbon of the same composition and size as in Example 1, cast by the same method, was annealed at 380° C. for 60 minutes in a N2 gas atmosphere in a magnetic field, and then laser irradiated. . Irradiation was carried out using a YAG pulsed laser beam with a beam diameter of 0.1 mm under conditions such that the spot diameter was 100 μm, and the beam was scanned in the width direction of the ribbon so that the spot spacing was 250 μm and the dot spacing was 5 mm. After laser irradiation, this thin strip is chemically etched to a total thickness of 2μ from both the front and back sides.
m removed. Note that the etching solution is 5 vol of hydrogen fluoride.
．． % hydrogen peroxide solution. When the iron loss of this ribbon was measured using a single plate tester, W13/50 was 0.065.
It was W/kg. This iron loss value is superior to the iron loss of 0.104 W/kg without etching.

Example 3 YAG was cast onto an amorphous alloy ribbon having a thickness of 65 μm and a width of 25 mm, which was cast in the same manner as in Example 1 except that the composition was the same as in Example 1 and the peripheral speed of the roll was 20 m/s. A pulsed laser was irradiated. The irradiation was carried out under conditions such that the spot diameter was 150 μm, and the beam was scanned so that the spot spacing was 300 μm and the dot row spacing was 8 mm in the width direction of the ribbon. After laser irradiation, the ribbon was annealed in a magnetic field at 380° C. for 60 minutes in N2 gas, and further etched by a total of 5 μm from both the front and back surfaces. The etching solution was the same as in Examples 1 and 2. When the iron loss of this ribbon was measured using a single plate tester, it was found that W
13/50 was 0.058W/kg. This iron loss value is 0.116W/k without etching.
This is an excellent value compared to g.

Example 4 Four slits each having the same composition as Example 1 and each having a width of 0.4 mm
Using nozzles arranged at mm intervals, the roll circumferential speed was 18 m.
An amorphous alloy ribbon with a thickness of 82 μm and a width of 25 mm, which was cast in the same manner as in Example 1 except that
After annealing in a magnetic field in N2 gas for 0 minutes, a total thickness of 10 μm was removed from both the front and back sides of the ribbon by etching. Grooves having a depth of 2 μm, a width of 50 μm, and an interval of 10 mm were formed in the ribbon in a direction parallel to the width of the ribbon. Iron loss W13/50 measured with a single plate tester is 0.073W
/kg. This iron loss value is superior to the iron loss value of 0.125 W/kg obtained by forming grooves in a Fe-based amorphous alloy ribbon of the same plate thickness of 72 μm without etching.

Example 5 A plate with the same composition and thickness as Example 4, cast by the same method, with a thickness of 82 μm.
m, an amorphous alloy ribbon with a width of 25 μm was heated at 400°C for 60 minutes,
After annealing in a magnetic field in N2 gas, a total thickness of 10 μm was removed from both the front and back surfaces of the ribbon by etching. The surface of this ribbon was scribed using a metal needle with a tip diameter of 30 μm to introduce linear strain at intervals of 10 mm parallel to the width direction of the ribbon. W13/50 measured with a veneer tester after introducing strain was 0.078 W/kg. This iron loss value is 0.132 when linear strain is introduced into the same 72 μm thick Fe-based amorphous alloy ribbon without etching.
This is an excellent value compared to W/kg.

[0023]

[Effect of the invention] The Fe-based amorphous alloy provided by the present invention is
The iron loss is significantly improved compared to conventional Fe-based amorphous alloys. Therefore, when this alloy is used for the iron core of power transformers, high frequency transformers, and yokes of magnetic circuits, it can reduce loss,
In other words, the effect of improving efficiency is noticeable. Furthermore, when used as a magnetic sensor, the sensitivity is significantly improved.

[Brief explanation of the drawing]

[Figure 1] Changes in iron loss (●) and changes in hysteresis loss (●) when the thickness of a 62 μm amorphous Fe80.5Si6.5 B12C1 alloy ribbon fabricated by the multi-slit nozzle method is removed by etching. ○). For comparison, a thin strip having the same composition and having a thickness of 30 μm was also examined in the same manner. ▲ indicates iron loss, △ indicates hysteresis loss.

FIG. 2 is a diagram showing the dependence of the iron loss improvement effect on the plate thickness when laser irradiation is applied to the amorphous alloy ribbon after etching.

FIG. 3 is a diagram showing the structure of a nozzle used to produce a thick amorphous alloy ribbon having a thickness of 45 μm or more.

FIG. 4 is a diagram showing the dependence of the laser irradiation effect on the plate thickness.

[Explanation of symbols]

a Double slit nozzle b Triple slit nozzle l, l1, l2 Slit interval W1,
W2, W3 Width of slit → direction of movement of cooling board

Claims (8)

[Claims] 1. In an Fe-based amorphous alloy ribbon having a thickness of 45 μm or more produced using a multi-slit nozzle, the surface layer of the amorphous alloy ribbon has at least 0.
An Fe-based amorphous alloy with excellent soft magnetic properties characterized by a hysteresis loss of 0.04 W/kg or less at a maximum magnetic flux density of 1.3 T by removing a thickness of 5 μm from both the front and back surfaces. Method for manufacturing thin strips. 2. The method for producing an Fe-based amorphous alloy ribbon with excellent soft magnetic properties according to claim 1, wherein the ribbon surface layer is removed by chemical etching. 3. An Fe-based amorphous alloy ribbon with excellent soft magnetic properties produced by the method according to claims 1 and 2. 4. By performing magnetic domain refining treatment on the Fe-based amorphous alloy ribbon having a plate thickness of 30 μm or more produced by the method according to claim 1, the iron loss at 50 Hz and 1.3 T can be reduced to 0. A method for producing an Fe-based amorphous alloy ribbon with excellent soft magnetic properties, characterized in that the magnetic strength is 0.8 W/kg or less. 5. The method for producing a Fe-based amorphous alloy ribbon with excellent soft magnetic properties according to claim 4, wherein the method of magnetic domain refining is pulsed laser irradiation. 6. The method for producing an Fe-based amorphous alloy ribbon with excellent soft magnetic properties according to claim 4, wherein the magnetic domain refining method is by forming grooves parallel to the width direction of the ribbon. . 7. The method for producing an Fe-based amorphous alloy ribbon with excellent soft magnetic properties according to claim 4, wherein the method of magnetic domain refining is the introduction of mechanical strain. 8. An Fe-based amorphous alloy ribbon with excellent soft magnetic properties produced by the method according to claim 4.